Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
  • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part

Definitions

• the invention relates to a new process for the preparation of chlorides of carboxylic acids from the corresponding carboxylic acids.
• the present invention fulfils this expectation and its subject is a process for the preparation of acyl chlorides with a reactant which is not highly toxic and which does not give rise to impurities.
• the process according to the invention is a process for the preparation of chlorides of carboxylic acids by reaction of tetrachloroethylene carbonate with the corresponding carboxylic acids, at a temperature of between 80° C. and 160° C.
• the reaction scheme is the following: ##STR5##
• Tetrachloroethylene carbonate which is used to implement the process according to the invention is a known compound. It can be easily prepared by a photochemical reaction of chlorine with ethylene carbonate, as described in U.S. Pat. No. 2,816,287: ##STR6##
• the carboxylic acids with which it is used to react are very numerous and diverse. They are to be found commercially or are prepared according to known methods.
• the acyl chlorides obtained are consequently very pure, free from interfering products.
• a linear or branched C 1 -C 30 alkyl radical which may contain one or more double or triple carbon-carbon bonds and one or more substituents chosen from halogen atoms and aryl, aryloxy, alkoxy, alkyloxycarbonyl, aryloxycarbonyl and 5- or 6-membered heterocyclic radicals, saturated or unsaturated, the hetero atom(s) being chosen from sulphur or oxygen atoms,
• a C 3 -C 7 cycloalkyl radical which may contain one or more carbon-carbon double bonds when it contains from 5 to 7 carbon atoms, and which may carry one or more substituents chosen from halogen atoms and alkyl, alkenyl, aryl, alkyloxycarbonyl and aryloxycarbonyl radicals,
• hetero atom(s) being chosen from sulphur, oxygen or nitrogen atoms, which may carry one or more substituents chosen from halogen atoms, alkyl or haloalkyl radicals comprising or not comprising one or more double or triple bonds, aryl, alkoxy, aryloxy, alkyloxycarbonyl and aryloxycarbonyl radicals and nitro and cyano groups,
• a 5- or 6-membered nonaromatic heterocyclic radical comprising one or more hetero atoms chosen from oxygen and sulphur, capable of comprising one or more double bonds and substituted or otherwise by one or more alkyl, alkyloxycarbonyl and aryloxycarbonyl radicals,
• n denotes an integer which can take the values 1 to 4.
• radical R denotes
• C 1 -C 20 alkyl radical which may contain one or more double or triple carbon-carbon bonds and one or more substituents chosen from chlorine, bromine or fluorine atoms and C 1 -C 4 alkoxy, phenyl, naphthyl, phenoxy, naphthoxy, C 1 -C 4 alkyloxycarbonyl, phenoxycarbonyl, furyl, pyranyl and thienyl radicals,
• a C 3 -C 6 cycloalkyl radical which may comprise a double bond when it contains from 5 to 6 carbon atoms and which may carry one or more substituents chosen from C 1 -C 5 alkyl and alkenyl radicals,
• hetero atom(s) being chosen from sulphur, oxygen or nitrogen atoms, comprising 5- or 6-membered heterocyclic rings, condensed or otherwise, and which may carry one or more substituents chosen from halogen atoms, C 1 -C 12 alkyl, fluoro- or chloroalkyl radicals comprising or not comprising one or more double or triple bonds, C 6 -C 10 aryl, C 1 -C 12 alkoxy, C 6 -C 10 aryloxy, C 1 -C 4 alkyloxycarbonyl and phenoxycarbonyl radicals, and nitro and cyano groups, in particular the phenyl, naphthyl,
• furyl benzofuryl, phenoxy and naphthoxy radical
• n denotes the value 1 or 2.
• acids which may be employed within the scope of the invention, there may be mentioned propionic, butyric, isobutyric, valeric, isovaleric, pivalic, hexanoic, octanoic, decanoic, lauric, palmitic, stearic, tricontanoic, undecylenic, acrylic, methacrylic, crotonic, isocrotonic, propargylic, vinylacetic, oleic, chloroacetic, dichloroacetic, trichloroacetic, bromoacetic, dibromoacetic, tribromoacetic, alpha-chloropropionic, alpha-chlorobutyric, malonic, succinic, adipic and sebacic acid, the monomethyl ester of malonic acid, the monomethyl ester of succinic acid, phenylacetic, phenyloxyacetic,beta-phenylpropionic,beta-phenyloxy
• Tetrachloroethylene carbonate is preferably added progressively to the reaction medium which has been heated and kept at the chosen temperature. It is generally employed in a quantity of between 0.50 and 0.75 equivalent per equivalent of acidic group to be converted, preferably between 0.52 and 0.6 equivalent.
• acyl chlorides of low boiling point or whose corresponding acids have a high melting point for example above 140° C.
• inert solvents chosen, for example, from chlorinated aliphatic solvents such as 1,2-dichloroethane, or aromatic solvents such as toluene, xylene, chlorobenzene and dichlorobenzenes.
• catalytic compounds may make it possible to shorten the reaction times and/or to lower the temperature.
• the catalysts are chosen from the catalysts which are already known and employed in the reactions for preparing chlorides of carboxylic acids, described earlier.
• tertiary amines and their hydrochlorides in particular pyridine and 4-N,N-dimethylpyridine (DMAP),
• quaternary ammonium salts and in particular chlorides and bromides, for example those of tetra-n-butyl and those of benzyltri-n-butyl,
• N,N-disubstituted amides in particular N,N-dimethylformamide and their reaction products with compounds such as PCl 3 , PCl 5 , POCl 3 , COCl 2 , SOCl 2 and (CO) 2 Cl 2 (Vilsmeier-Haack salts),
• tetrasubstituted ureas in particular tetramethylurea and tetrabutylurea, and their reaction products with the compound agents such as PCl 3 , PCl 5 , POCl 3 , COCl 2 , SOCl 2 and (CO) 2 Cl 2 ,
• hexaalkylphosphoramides such as hexamethylphosphorotriamide (HMPT)
• hexaalkylguanidinium salts in particular chlorides, and their hydrochlorides, as described in Patent Application EP No. 213,976, in particular hexamethyl- and hexabutylguanidinium chlorides.
• the quantity of catalyst which is added is generally between 10 -4 and 10 -1 equivalent per equivalent of acidic group to be converted.
• the chlorination temperature is between 80° and 160° C. In the absence of a catalyst the reaction is generally performed at a temperature of between 110° and 160° C., preferably between 120° C. and 160° C. When a catalyst is employed, the reaction is generally performed between 80° and 150° C. and preferably between 100° and 135° C.
• the reaction time is generally between 1 and 4 hours.
• Acyl chlorides are well-known compounds whose applications are numerous. They are employed, for example, as synthesis intermediates for the preparation of esters, amides, peresters and peroxides, polymeric compounds, pesticidal and pharmaceutical products and in the papermaking industry.
• the carboxylic acid, the solvent where appropriate, and the catalyst are introduced into a reactor equipped with a stirrer, a thermometer and a reflux condenser.
• the reaction mixture is heated to the temperature indicated and 0.50 to 0.6 equivalent of tetrachloroethylene carbonate (TCEC) per acidic group to be converted is introduced slowly while the temperature is maintained.
• TCEC tetrachloroethylene carbonate
• the acyl chloride is separated by distillation from the residual tetrachloroethylene carbonate, if necessary.

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• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1987
  • 1987-11-05 FR FR8715344A patent/FR2622885B1/fr not_active Expired - Lifetime
• 1988
  • 1988-10-10 IE IE306488A patent/IE61589B1/en unknown
  • 1988-10-17 US US07/258,634 patent/US4966995A/en not_active Expired - Lifetime
  • 1988-10-17 IL IL88063A patent/IL88063A/xx not_active IP Right Cessation
  • 1988-11-02 DE DE8888402738T patent/DE3862848D1/de not_active Expired - Lifetime
  • 1988-11-02 AT AT88402738T patent/ATE63536T1/de not_active IP Right Cessation
  • 1988-11-02 ES ES88402738T patent/ES2022677B3/es not_active Expired - Lifetime
  • 1988-11-02 EP EP88402738A patent/EP0315517B1/fr not_active Expired - Lifetime
  • 1988-11-04 HU HU885708A patent/HU200315B/hu not_active IP Right Cessation
  • 1988-11-04 JP JP63277609A patent/JPH0822824B2/ja not_active Expired - Fee Related
  • 1988-11-04 CA CA000582313A patent/CA1312614C/fr not_active Expired - Fee Related

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